US3966824A - P,P'-Disubstituted α-trichloromethylbenzylphenyl ethers - Google Patents

P,P'-Disubstituted α-trichloromethylbenzylphenyl ethers Download PDF

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US3966824A
US3966824A US05/528,351 US52835174A US3966824A US 3966824 A US3966824 A US 3966824A US 52835174 A US52835174 A US 52835174A US 3966824 A US3966824 A US 3966824A
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sub
compounds
ddt
trichloromethylbenzylphenyl
ethers
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Robert L. Metcalf
Inder Kapoor
Asha Hirwe
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University of Illinois Foundation
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University of Illinois Foundation
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system

Definitions

  • the present invention relates to new compositions of matter.
  • it concerns p,p'-disubstituted ⁇ -trichloromethylbenzylphenyl ethers some of which exhibit selective or nonselective insecticidal and/or larvicidal properties, as well as greater or lesser degrees of biodegradability.
  • the p,p'-disubstituted ⁇ -trichloromethylbenzylphenyl ethers of the present invention are a novel class of compounds. Their properties are such that they exhibit utilities as selective or nonselective insecticides and/or larvicides. In addition, many of the members of the class of compounds of the present invention also exhibit properties of biodegradability. In view of the fact that DDT [1, 1, 1 trichloro-2,2-bis(p-chlorophenyl)ethane], the insecticide in most widespread use today, is not biodegradable, these properties take on added importance by serving to minimize one of the greatest deficiencies of prior art insecticides.
  • MFO multifunction oxidases
  • methoxychlor [1,1,1-trichloro-,2,2-bis(p-methoxyphenyl)ethane] and methiochlor [1,1,1-trichloro-2,2-bis-(p-methiophenyl) ethane] are readily attacked by MFO enzymes, which metabolically convert or boidegrade such analogs into environmentally acceptable products which are rapidly eliminated by animals.
  • methoxychlor is an example of a biodegradable insecticide which is not generally accumulated in animal tissues and is, thus, a more prudent choice than DDT for a variety of uses where environmental pollution is an important factor.
  • metoxychlor and other known symmetrical DDT analogs e.g., methylchlor [1,1,1-trichloro-2,2-bis(p-methylphenyl)ethane] and methiochlor
  • methylchlor [1,1,1-trichloro-2,2-bis(p-methylphenyl)ethane] and methiochlor while exhibiting satisfactory insecticidal activity towards certain species of insects, exhibit considerably less insecticidal activity than DDT towards other species of insects.
  • the compounds of the present invention are p,p'-disubstituted ⁇ -trichloromethylbenzylphenyl ethers.
  • the two p,p' substituent groups are chosen from the group consisting of Cl, CH 3 , CH 3 O, and C 2 H 5 O.
  • These compounds are biodegraded and metabolically converted to environmentally acceptable products by attack by MFO enzymes on the various substituents of the aryl rings to produce water-partitioning moieties.
  • further biodegradability is provided by separation of the two aryl rings by cleavage of the -O-CH(CCl 3 )-bond, which is not present in DDT or its symmetrical or asymmetrical analogues.
  • the presence of an oxygen atom between the two aryl rings of the compounds of the invention provides a means of increasing biodegradability ad does not destroy toxicity to insects.
  • Such p,p'-disubstituted ⁇ -trichloromethylbenzylphenyl ethers may be synthesized by condensing the appropriate ⁇ -trichloromethylbenzyl alcohol (DDT-type carbinol) with equimolar quantities of the appropriate phenol using concentrated sulfuric acid or polyphosphoric acid as the condensing agent.
  • DDT-type carbinol ⁇ -trichloromethylbenzyl alcohol
  • the compounds of the present invention were tested for insecticidal activity by standard methods, and compared with the insecticidal activities of DDT and symmetrical analogs of DDT, such as methoxychlor.
  • Toxicological methods for the determination of the topical LD 50 values to adult female S NAIDM and P SR houseflies, Musca domestica L. and to Phormia regina, and LC 50 values to clex pipiens quinquefas ciatus Say, and Anopheles albimanus Weid mosquitoes were described by Metcalf et al., 44 Bull. World Health Org. 363 (1971).
  • the data of Table II indicate the insect toxicity of 9 different ⁇ -trichloromethylbenzylphenyl ethers to Musca domestica (S NAIDM and R SP strains), Phormia regina, and to Culex fatigans and Anopheles albimanus.
  • the compounds with the highest intrinsic toxicity were CH 3 O, OC 2 H 5 (VII), Cl, OC 2 H 5 (VI), and C 2 H 5 O, OC 2 H 5 (IV).
  • the CH 3 O, OCH 3 compound (II) had the largest SR value in both susceptible and resistant houseflies (22->8.7), indicating rapid detoxication, while the Cl, OC 2 H 5 compound (VI) had the lowest SR values (1.9-2.5).
  • the most effective insecticide generally was VI ( ⁇ -trichloromethyl-p-ethoxybenzyl p-chlorophenyl ether) which had the lowest LD 50 values to the housefly and was only slightly less toxic to Phormia than the p,p'-diethoxy compound IV and to mosquito larvae than compound I.
  • Toxicity in the symmetrical substituents was in the general order of C 2 H 5 O > Cl > CH 3 O > CH 3 .
  • the synergistic ratios or SR values (LD 50 alone/ LD 50 synergized with piperonyl butoxide) shown in Table II indicate the role of the multifunction oxidase (MFO) in detoxifying the individual compounds. Since piperonyl butoxide serves to block the action of MFO, the synergized LD 50 values express the intrinsic toxicity of the compounds. With the detoxifying action of MFO enzymes blocked, the intrinsic toxicity of the compounds can thus be measured.
  • MFO multifunction oxidase
  • the compounds with the highest intrinsic toxicity were CH 3 O, C 2 H 5 (VII), Cl, C 2 H 5 O (VI) C 2 H 5 O, OC 2 H 5 (IV) and CH 3 O, CH 3 O (II), having synergized LD 50 values of 5.0, 9.5, 13.0, and 14.0 respectively.
  • Compounds IV and VII were quite toxic to Phormia, which is dificient in MFO, with synergized LD 50 values of 16.5 and 16.0 respectively.
  • Cl (I) was the most toxic, with an LC 50 ppm of 0.035 and 0.014 for Culex fatigans and Anopheles albimanus respectively.

Abstract

P,P'-DISUBSTITUTED α-TRICHLOROMETHYLBENZYLPHENYL ETHERS ARE A NEW CLASS OF COMPOUNDS WHICH SHOW VARYING DEGREES OF UTILITY AS SELECTIVE OR NONSELECTIVE BIODEGRADABLE INSECTICIDES AND/OR LARVICIDES.

Description

This is a division of application Ser. No. 318,206, filed Dec. 26, 1972 and now U.S. Pat. No. 3,894,092.
SUMMARY OF THE INVENTION
The present invention relates to new compositions of matter. In particular, it concerns p,p'-disubstituted α-trichloromethylbenzylphenyl ethers some of which exhibit selective or nonselective insecticidal and/or larvicidal properties, as well as greater or lesser degrees of biodegradability.
BACKGROUND OF THE INVENTION
The p,p'-disubstituted α-trichloromethylbenzylphenyl ethers of the present invention are a novel class of compounds. Their properties are such that they exhibit utilities as selective or nonselective insecticides and/or larvicides. In addition, many of the members of the class of compounds of the present invention also exhibit properties of biodegradability. In view of the fact that DDT [1, 1, 1 trichloro-2,2-bis(p-chlorophenyl)ethane], the insecticide in most widespread use today, is not biodegradable, these properties take on added importance by serving to minimize one of the greatest deficiencies of prior art insecticides.
There is growing concern about the continuing liberation of vast quantities of DDT into the environment. The very qualities which make DDT such an effective contact or residual insecticide, i.e., its very low water solubility and high lipid solubility, caused by the non-polarity of the DDT molecule, result in its accumulation in the fatty or lipid tissues of animals. These properties result in ever increasing concentrations in the tissues of carnivorous animals at the upper ends of food chains. The problems associated with this magnification phenomenon are further intensified by the enzymatic metabolic conversion of DDT to the even more stable dehydrochlorination product, DDE [1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene].
Drug metabolizing enzymes, known as multifunction oxidases (MFO), which play a dominant role in detoxifying insecticides in both insects and higher animals, such as birds, fish, and mammals do not function on DDT and its metabolic derivatives DDE and DDD (or TDE) [1,1-dichloro-2,2-bis(p-chlorophenyl)ethane] as substrates. This single factor accounts for their storage and accumulation in animal tissues, especially at the higher ends of food chains.
Certain known symmetrical DDT analogs, such as methoxychlor [1,1,1-trichloro-,2,2-bis(p-methoxyphenyl)ethane] and methiochlor [1,1,1-trichloro-2,2-bis-(p-methiophenyl) ethane] are readily attacked by MFO enzymes, which metabolically convert or boidegrade such analogs into environmentally acceptable products which are rapidly eliminated by animals. Thus, methoxychlor is an example of a biodegradable insecticide which is not generally accumulated in animal tissues and is, thus, a more prudent choice than DDT for a variety of uses where environmental pollution is an important factor. However, metoxychlor and other known symmetrical DDT analogs (e.g., methylchlor [1,1,1-trichloro-2,2-bis(p-methylphenyl)ethane] and methiochlor), while exhibiting satisfactory insecticidal activity towards certain species of insects, exhibit considerably less insecticidal activity than DDT towards other species of insects.
One attempt to remedy the problems of the prior art is disclosed in the copending application of Metcalf et al., "Insecticidal Biodegradable Analogues of DDT," Ser. No. 147,241, filed May 26, 1971, and having a common assignee with the present application. These asymmetrical analogues of DDT have in general proved to be biodegradable and effective as insecticides. The compounds in accordance with the present invention, however, offer a mechanism of molecular cleavage of the -O-CH(CCl.sub. 3)-bonds, whereby biodegradability may be increased. In addition to biodegradability, certain of the compounds of the present invention offer outstanding toxicity as either selective or non-selective insecticides. The compounds of the present invention are further distinguished from prior art insecticides in that they breakdown upon prolonged exposure to sunlight, which would prove to be beneficial in applications where persistence of the insecticide is either not necessary or undesirable.
DESCRIPTION OF THE INVENTION
It has been found from metabolic studies on insects, and mice, using a model ecosystem and the methods described in Kapoor, et al., 18(6) J.Agr., Food Chem. 1145 (1970), Metcalf, et al., J. Environ. Sci. Technol. 709 (1971) and also in the copending application of Metcalf et al., "Insecticidal Biodegradable Analogues of DDT", Ser. No. 147,241, filed May 26, 1971, and having a common assignee with the present application, that certain p,p'-disubstituted α-trichloromethylbenzylphenyl ethers with various substituent groups are readily attacked by multifunction oxidase (MFO) enzymes, and thus are substantially biodegradable. Insecticidal activity studies involving both DDT resistant and regular strains of house flies, the blow fly, various types of mosquitoes and other insects have further indicated that the compounds of the present invention are effective insecticides.
The compounds of the present invention are p,p'-disubstituted α-trichloromethylbenzylphenyl ethers. Preferably, the two p,p' substituent groups are chosen from the group consisting of Cl, CH3, CH3 O, and C2 H5 O. These compounds are biodegraded and metabolically converted to environmentally acceptable products by attack by MFO enzymes on the various substituents of the aryl rings to produce water-partitioning moieties. Also, further biodegradability is provided by separation of the two aryl rings by cleavage of the -O-CH(CCl3)-bond, which is not present in DDT or its symmetrical or asymmetrical analogues. The presence of an oxygen atom between the two aryl rings of the compounds of the invention provides a means of increasing biodegradability ad does not destroy toxicity to insects.
Such p,p'-disubstituted α-trichloromethylbenzylphenyl ethers may be synthesized by condensing the appropriate α-trichloromethylbenzyl alcohol (DDT-type carbinol) with equimolar quantities of the appropriate phenol using concentrated sulfuric acid or polyphosphoric acid as the condensing agent.
EXAMPLE I
α-trichloromethyl-p-chlorobenzyl alcohol, 5.0g, was stirred with p-chlorophenol, 2.6g, and sulfuric acid, 35 ml, was added dropwise. After 2 hrs. of stirring, the mixture was poured onto ice and extracted with ether. After drying with sodium sulfate, the ether was removed under vacuum and the residue was recrystallized from ethanol to give α-trichloromethyl-p-chlorobenzyl p-chlorophenyl ether, mp 101°C. This method of synthesis is referred to in Table I as method A.
EXAMPLE II
α-trichloromethyl-p-methoxybenzyl alcohol, 5.0g, and p-methoxyphenol, 2.48g, were added to a mixture of phosphorus pentoxide, 18g, and phosphoric acid, 12 ml, and heated for 1 hr. on the steam bath. After standing overnight, ice was added and the mixture extracted with ether. The product was purified by column chromatography on silica gel and eluted with 5% ether in petroleum ether (60°-68°C) to give α-trichloromethyl-p-methoxybenzyl p-methoxyphenyl ether, mp 90°C. This method of synthesis is referred to in Table I as method B.
Employing similar techniques, other compounds of the present invention were prepared. The properties and structures are set forth in Table I.
The compounds of the present invention were tested for insecticidal activity by standard methods, and compared with the insecticidal activities of DDT and symmetrical analogs of DDT, such as methoxychlor. Toxicological methods for the determination of the topical LD50 values to adult female SNAIDM and PSR houseflies, Musca domestica L. and to Phormia regina, and LC50 values to clex pipiens quinquefas ciatus Say, and Anopheles albimanus Weid mosquitoes were described by Metcalf et al., 44 Bull. World Health Org. 363 (1971). The methods for evaluation of metabolism by mouse liver homogenate and by female RSP housefly and salt-marsh caterpillar larvae Estigmene acrea Drury, were described by Metcalf et al., 5 J. Environ. Sci. Tech. 709 (1971). The results are detailed in Table II.
                                  TABLE I                                 
__________________________________________________________________________
Chemical Structures and Properties of α-Trichloromethylbenzylphenyl 
Ethers                                                                    
              Method                                                      
              of                                                          
R.sup.1                                                                   
     R.sup.2                                                              
          mp °C                                                    
              synthesis                                                   
                     nmr data, α δ ppm                        
__________________________________________________________________________
Cl   Cl   101 A     α-H 5.4 (s)                                     
CH.sub.3 O                                                                
     CH.sub.3 O                                                           
           90 B     α-H 5.36 (s), OCH.sub.3 3.36                    
                     (s), 3.8 (s)                                         
CH.sub.3                                                                  
     CH.sub.3                                                             
          Liquid                                                          
              B     α-H 5.41 (s), CH.sub.3 2.33 (s),                
                     CH.sub.3 2.83 (s)                                    
C.sub.2 H.sub.5 O                                                         
     C.sub.2 H.sub.5 O                                                    
          Liquid                                                          
              B     α-H 5.21 (s), OCH.sub.2 3.61-                   
                     4.13 (m), CH.sub.3 1.2-1.5                           
                     (m)                                                  
Cl   CH.sub.3 O                                                           
           90 B     α-H 5.43 (s), OCH.sub.3 3.43 (s)                
Cl   C.sub.2 H.sub.5 O                                                    
          Liquid                                                          
              A     α-H 5.43 (s), OCH.sub.2 3.83-                   
                     4.2 (q), CH.sub.3 1.26-1.5 (t)                       
CH.sub.3 O                                                                
     C.sub.2 H.sub.5 O                                                    
           80 B     α-H 5.43 (s), OCH.sub.2 3.85-                   
                     4.2 (q), CH.sub.3 1.3-1.5 (t),                       
                     OCH.sub.3 3.73 (s)                                   
CH.sub.3                                                                  
     C.sub.2 H.sub.5 O                                                    
          Liquid                                                          
              B     α-H 5.32 (s), CH.sub.3 2.16 (s),                
                     OCH.sub.2 3.75-4.1 (q) CH.sub.3                      
                     1.2-1.46 (t)                                         
CH.sub.3                                                                  
     CH.sub.3 O                                                           
          142 B     α-H 5.62, CH.sub.3 2.33 (s),                    
                     OCH.sub.3 3.83 (s)                                   
__________________________________________________________________________

                                  TABLE II                                
__________________________________________________________________________
Toxicity of α-Trichloromethylbenzylphenyl Ethers to Insects         
Topical LD.sub.50 μg per g for                                         
__________________________________________________________________________
           Musca domestica                           LC.sub.50 ppm        
                                                      Culex               
                                                         Anopheles        
Substituents                                                              
           SNAIDM         R.sub.sp     Phormia regina                     
                                                     fatigans             
                                                         albimanus        
R.sup.1                                                                   
       R.sup.2                                                            
           Alone pb  SR   Alone                                           
                              pb   SR  Alone  pb  SR larvae               
                                                         larvae           
__________________________________________________________________________
I  Cl  Cl  90    90  1.0  >500                                            
                              180  >3.6                                   
                                       >250  >250 -- 0.035                
                                                         0.014            
II CH.sub.3 O                                                             
       CH.sub.3 O                                                         
           300   14.0                                                     
                     22   >500                                            
                              57.5 >8.7                                   
                                       125     82.5                       
                                                  1.5                     
                                                     0.51                 
                                                         0.10             
III                                                                       
   CH.sub.3                                                               
       CH.sub.3                                                           
           265   90  2.9  >500                                            
                              145  >3  135     100                        
                                                  1.35                    
                                                     0.12                 
                                                         0.18             
IV C.sub.2 H.sub.5 O                                                      
       C.sub.2 H.sub.5 O                                                  
           27.0  13.0                                                     
                     2.1    42                                            
                              24.5 1.7 16.5    16.5                       
                                                  1.0                     
                                                     0.11                 
                                                         0.07             
V  Cl  CH.sub.3 O                                                         
           107.5 17.0                                                     
                     6.3    130                                           
                              82.5 1.6 205     115                        
                                                  1.8                     
                                                     0.14                 
                                                         0.038            
VI Cl  C.sub.2 H.sub.5 O                                                  
           18.5  9.5 1.9    31                                            
                              12.5 2.5 31.2    31.2                       
                                                  1.0                     
                                                     0.067                
                                                         0.044            
VII                                                                       
   CH.sub.3 O                                                             
       C.sub.2 H.sub.5 O                                                  
           45.0  5.0 9.0    90                                            
                              14.0 6.4 30.0    16.0                       
                                                  1.9                     
                                                     0.14                 
                                                         0.034            
VIII                                                                      
   CH.sub.3                                                               
       C.sub.2 H.sub.5 O                                                  
           72.5  20.5                                                     
                     3.5    65                                            
                              22.0 2.9 46.2    30.0                       
                                                  1.5                     
                                                     0.18                 
                                                         0.066            
IX CH.sub.3                                                               
       CH.sub.3 O                                                         
           >500  39.0                                                     
                     >13  >500                                            
                              135  >4  >250  >250 -- 0.65                 
                                                         >1.0             
__________________________________________________________________________
Compounds of the Present Invention are Effective Insecticides
The data of Table II indicate the insect toxicity of 9 different α-trichloromethylbenzylphenyl ethers to Musca domestica (SNAIDM and RSP strains), Phormia regina, and to Culex fatigans and Anopheles albimanus. The compounds with the highest intrinsic toxicity were CH3 O, OC2 H5 (VII), Cl, OC2 H5 (VI), and C2 H5 O, OC2 H5 (IV). The CH3 O, OCH3 compound (II) had the largest SR value in both susceptible and resistant houseflies (22->8.7), indicating rapid detoxication, while the Cl, OC2 H5 compound (VI) had the lowest SR values (1.9-2.5).
The most effective insecticide generally was VI (α-trichloromethyl-p-ethoxybenzyl p-chlorophenyl ether) which had the lowest LD50 values to the housefly and was only slightly less toxic to Phormia than the p,p'-diethoxy compound IV and to mosquito larvae than compound I. Toxicity in the symmetrical substituents was in the general order of C2 H5 O > Cl > CH3 O > CH3.
The synergistic ratios or SR values (LD50 alone/ LD50 synergized with piperonyl butoxide) shown in Table II indicate the role of the multifunction oxidase (MFO) in detoxifying the individual compounds. Since piperonyl butoxide serves to block the action of MFO, the synergized LD50 values express the intrinsic toxicity of the compounds. With the detoxifying action of MFO enzymes blocked, the intrinsic toxicity of the compounds can thus be measured. For the Musca domestica SNAIDM, the compounds with the highest intrinsic toxicity were CH3 O, C2 H5 (VII), Cl, C2 H5 O (VI) C2 H5 O, OC2 H5 (IV) and CH3 O, CH3 O (II), having synergized LD50 values of 5.0, 9.5, 13.0, and 14.0 respectively. Compounds IV and VII were quite toxic to Phormia, which is dificient in MFO, with synergized LD50 values of 16.5 and 16.0 respectively. As a larvicide Cl, Cl (I) was the most toxic, with an LC50 ppm of 0.035 and 0.014 for Culex fatigans and Anopheles albimanus respectively.
Employing the techniques disclosed in Metcalf et al., 5 J. Environ. Sci. Technol. 709 (1971), the compounds of the present invention have been shown to be biodegradable.
The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom as modifications will be obvious to those skilled in the art.

Claims (5)

What is claimed is:
1. Insecticides having the formula ##SPC1##
where R1 and R2 are selected from the group consisting of substituents Cl, CH3 , CH3 O, and C2 H5 O, provided that at least one of R1 and R2 in Cl or CH3 .
2. An insecticide as claimed in claim 1 wherein R1 is Cl.
3. An insecticide as claimed in claim 1 wherein R1 is CH3.
4. An insecticide as claimed in claim 1 wherein R2 is Cl.
5. An insecticide as defined by claim 1 wherein R2 is CH3.
US05/528,351 1972-12-26 1974-11-29 P,P'-Disubstituted α-trichloromethylbenzylphenyl ethers Expired - Lifetime US3966824A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678811A (en) * 1984-10-17 1987-07-07 Schering Aktiengesellschaft Substituted benzylethers, pesticides containing these compounds and method for their preparation
EP0504812A2 (en) * 1991-03-19 1992-09-23 Sumitomo Chemical Company, Limited Aromatic compounds, their production processes and their compositions for the control of insect pests

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787505A (en) * 1971-05-26 1974-01-22 Univ Illinois Insecticidal biodegradable analogues of ddt

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787505A (en) * 1971-05-26 1974-01-22 Univ Illinois Insecticidal biodegradable analogues of ddt

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4678811A (en) * 1984-10-17 1987-07-07 Schering Aktiengesellschaft Substituted benzylethers, pesticides containing these compounds and method for their preparation
EP0504812A2 (en) * 1991-03-19 1992-09-23 Sumitomo Chemical Company, Limited Aromatic compounds, their production processes and their compositions for the control of insect pests
EP0504812A3 (en) * 1991-03-19 1992-10-28 Sumitomo Chemical Company, Limited Aromatic compounds, their production processes and their compositions for the control of insect pests
US5302619A (en) * 1991-03-19 1994-04-12 Sumitomo Chemical Company, Limited Aromatic compounds, their production processes and their compositions for the control of insect pests

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